WO2021024328A1 - 接着剤組成物、熱硬化性接着シート及びプリント配線板 - Google Patents

接着剤組成物、熱硬化性接着シート及びプリント配線板 Download PDF

Info

Publication number
WO2021024328A1
WO2021024328A1 PCT/JP2019/030600 JP2019030600W WO2021024328A1 WO 2021024328 A1 WO2021024328 A1 WO 2021024328A1 JP 2019030600 W JP2019030600 W JP 2019030600W WO 2021024328 A1 WO2021024328 A1 WO 2021024328A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
styrene
mass
parts
epoxy resin
Prior art date
Application number
PCT/JP2019/030600
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
山本　潤
利之 峯岸
和宏 伊達
Original Assignee
デクセリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to CN201980098839.4A priority Critical patent/CN114174459B/zh
Priority to US17/629,932 priority patent/US20220298396A1/en
Priority to PCT/JP2019/030600 priority patent/WO2021024328A1/ja
Priority to JP2021538547A priority patent/JP7322153B2/ja
Priority to KR1020227002763A priority patent/KR20220024998A/ko
Publication of WO2021024328A1 publication Critical patent/WO2021024328A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/303—Surface mounted components, e.g. affixing before soldering, aligning means, spacing means
    • H05K3/305—Affixing by adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether

Definitions

  • This technology relates to adhesive compositions, thermosetting adhesive sheets and printed wiring boards.
  • polyphenylene ether has many advantages as a substrate material having low dielectric properties, but it has a drawback that it is inferior in bending resistance because it has a very high melting point (softening point) and is hard at room temperature.
  • softening point a melting point
  • the bending resistance tends to be inferior.
  • the present technology has been proposed in view of such conventional circumstances, and provides an adhesive composition having a low dielectric constant and dielectric loss tangent and good bending resistance, a thermosetting adhesive sheet, and a printed wiring board. To do.
  • the adhesive composition according to the present technology contains 75 to 90 parts by mass of a styrene-based elastomer and 3 to 25 parts by mass of a modified polyphenylene ether resin having a polymerizable group at the terminal with respect to a total of 100 parts by mass of the adhesive composition.
  • a total of 10 parts by mass or less of the epoxy resin and the epoxy resin curing agent is contained, and the styrene ratio of the styrene-based elastomer is less than 30%.
  • thermosetting adhesive sheet In the thermosetting adhesive sheet according to the present technology, a thermosetting adhesive layer made of the above-mentioned adhesive composition is formed on a base material.
  • the wiring pattern side of the resin substrate with wiring provided with the base material and the wiring pattern and the coverlay are laminated via the cured product of the adhesive composition described above.
  • FIG. 1 is a cross-sectional view showing a configuration example of a printed wiring board.
  • FIG. 2 is a cross-sectional view showing a configuration example of a multilayer printed wiring board.
  • FIG. 3 is a plan view showing a configuration example of the TEG used in the bending resistance test.
  • FIG. 4 is a perspective view showing a measuring device used for the bending resistance test.
  • the values of the weight average molecular weight and the number average molecular weight of the components described below refer to the values calculated from the standard polystyrene-equivalent molecular weight measured by the gel permeation chromatography (GPC) method.
  • the adhesive composition according to the present technology is a thermosetting adhesive composition, and the styrene-based elastomer (component A) is 75 to 90 parts by mass with respect to 100 parts by mass of the total of the adhesive composition.
  • a total of 3 to 25 parts by mass of a modified polyphenylene ether resin having a polymerizable group at the terminal (component B; hereinafter, also simply referred to as a modified polyphenylene ether resin), an epoxy resin (component C), and an epoxy resin curing agent (component D). It contains 10 parts by mass or less.
  • the styrene ratio of the styrene-based elastomer is less than 30%.
  • the dielectric constant and the dielectric loss tangent are low even after thermosetting, and the glass transition temperature of the adhesive composition after curing can be adjusted to be low (for example, in the range of -40 to 40 ° C.). Therefore, it is possible to obtain an adhesive composition having good bending resistance even after thermosetting.
  • Such an adhesive composition can be suitably used as, for example, an adhesive (interlayer adhesive) for a flexible printed wiring board.
  • the styrene-based elastomer is a copolymer of styrene and an olefin (for example, a conjugated diene such as butadiene or isoprene) and / or a hydrogenated product thereof.
  • the styrene-based elastomer is a block copolymer having styrene as a hard segment and conjugated diene as a soft segment.
  • styrene-based elastomers examples include styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene block copolymers, styrene / ethylene / butylene / styrene block copolymers, and styrene / ethylene / propylene / styrene block copolymers. Examples include coalescence, styrene / butadiene block copolymers and the like.
  • styrene / ethylene / butylene / styrene block copolymers styrene / ethylene / propylene / styrene block copolymers, and styrene / butadiene block copolymers (hydrogenated) in which the double bond of the conjugated diene component is eliminated by hydrogenation.
  • styrene-based elastomer Also referred to as a styrene-based elastomer
  • the weight average molecular weight of the styrene-based elastomer is preferably 100,000 or more, more preferably 100,000 to 150,000, and even more preferably 110,000 to 150,000. With such a configuration, the peel strength (connection reliability) and heat resistance can be further improved.
  • the styrene ratio in the styrene-based elastomer is preferably less than 30%, more preferably 5 to 30%, further preferably 5 to 25%, and particularly preferably 10 to 20%.
  • the glass transition temperature of the adhesive composition after curing can be adjusted in the range of, for example, -40 to 40 ° C., so that the bending resistance is improved. ..
  • the peel strength (connection reliability) and heat resistance can be improved.
  • the glass transition temperature of the adhesive composition after curing becomes high, for example, 100 ° C. or more, so that the bending resistance tends to deteriorate.
  • the styrene-based elastomer has a weight average molecular weight of 100,000 or more (more preferably 110,) from the viewpoint of adjusting the glass transition temperature of the adhesive composition after curing to a low range and improving bending resistance. It is preferable to use a styrene-based elastomer having a styrene ratio of 000 to 150,000) and a styrene ratio of 5 to 25%.
  • styrene-based elastomer examples include Toughtech H1221 (Mw120,000, styrene ratio 12%), Toughtech H1062 (Mw116,000, styrene ratio 18%), Toughtech P1083 (Mw103,000, styrene ratio 20%), Toughtech M1943. (Mw100,000, styrene ratio 20%, manufactured by Asahi Kasei Corporation), Hybler 7125 (Mw110,000, styrene ratio 20%, manufactured by Kuraray Co., Ltd.).
  • Tough Tech H1221 and Hybler 7125 are preferable from the viewpoint of molecular weight and styrene ratio.
  • the content of the styrene-based elastomer in the adhesive composition is 75 to 90 parts by mass and 80 to 90 parts by mass with respect to 100 parts by mass in total of component A, component B, component C and component D. May be good. If the content of the styrene-based elastomer is less than 75 parts by mass, the bending resistance tends to be inferior. Further, when the content of the styrene-based elastomer exceeds 90 parts by mass, the content of other components (for example, component B) is relatively small, so that the heat resistance tends to be inferior.
  • the styrene-based elastomer may be used alone or in combination of two or more.
  • the modified polyphenylene ether resin has a polyphenylene ether chain in the molecule and has a polymerizable group at the terminal.
  • the modified polyphenylene ether resin preferably has at least two or more epoxy groups and ethylenically unsaturated bonds as polymerizable groups in one molecule.
  • the modified polyphenylene ether resin has an epoxy group and an ethylenically unsaturated bond (for example, (meth) acryloyl group) at both ends. , Vinyl benzyl group).
  • the polyphenylene ether resin not modified by the compound having a polymerizable group that is, the polyphenylene ether resin having a hydroxyl group at the terminal is too polar, has poor compatibility with the above-mentioned styrene-based elastomer, and has an adhesive composition. It is not preferable because it may not be possible to form a film.
  • the modified polyphenylene ether resin having vinylbenzyl groups at both ends which is an example of the modified polyphenylene ether resin, is, for example, the terminal of the bifunctional phenylene ether oligomer obtained by oxidizing coupling a bifunctional phenol compound and a monofunctional phenol compound. It is obtained by converting a phenolic hydroxyl group into vinylbenzyl ether.
  • the weight average molecular weight (or number average molecular weight) of the modified polyphenylene ether resin is the compatibility with the above-mentioned styrene-based elastomer, and the resin substrate with wiring provided with the substrate and the wiring pattern via the cured product of the adhesive composition. From the viewpoint of step followability when the wiring pattern side and the coverlay are heat-cured (pressed), the ratio is preferably 1,000 to 3,000.
  • modified polyphenylene ether resin examples include OPE-2St (modified polyphenylene ether resin having vinylbenzyl groups at both ends), OPE-2Gly (modified polyphenylene ether resin having epoxy groups at both ends), and OPE-2EA (both).
  • a modified polyphenylene ether resin having an acryloyl group at the terminal, manufactured by Mitsubishi Gas Chemicals, Inc.), a Noyl SA9000 (modified polyphenylene ether resin having a methacryloyl group at both ends, manufactured by SABIC) and the like can be used.
  • the content of the modified polyphenylene ether resin in the adhesive composition is 3 to 25 parts by mass and 5 to 20 parts by mass with respect to 100 parts by mass in total of component A, component B, component C and component D. Is preferable.
  • the content of the modified polyphenylene ether resin exceeds 25 parts by mass, the glass transition temperature of the adhesive composition after curing becomes high, so that the bending resistance tends to be inferior. Further, by setting the content of the modified polyphenylene ether resin to 5 parts by mass or more, the heat resistance can be further improved.
  • the polyphenylene ether resin may be used alone or in combination of two or more.
  • the epoxy resin is, for example, an epoxy resin having a naphthalene skeleton, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin, a siloxane type epoxy resin, a biphenyl type epoxy resin, or a glycidyl ester type.
  • examples thereof include epoxy resins, glycidylamine type epoxy resins, and hidden-in type epoxy resins.
  • the epoxy resin is preferably an epoxy resin having a naphthalene skeleton, a bisphenol A type epoxy resin, or a bisphenol F type epoxy resin, which is liquid at room temperature, from the viewpoint of film moldability.
  • the epoxy resin may be used alone or in combination of two or more.
  • the epoxy resin curing agent is a catalyst that accelerates the curing reaction of the epoxy resin described above.
  • the epoxy resin curing agent for example, imidazole-based, phenol-based, amine-based, acid anhydride-based, organic peroxide-based, and the like can be used.
  • the epoxy resin curing agent is preferably a curing agent having potential from the viewpoint of storage stability (life) of the adhesive composition at room temperature, and is an encapsulated imidazole-based curing agent having potential. More preferably, it is a curing agent. By improving the storability at room temperature, it is possible to more easily manage the supply and use of the adhesive composition.
  • the epoxy resin curing agent a microcapsule type latent curing agent having a latent imidazole modified product as a core and its surface coated with polyurethane can be used.
  • a commercially available product for example, Novacure 3941 (manufactured by Asahi Kasei E-Materials Co., Ltd.) can be used.
  • the epoxy resin curing agent may be used alone or in combination of two or more.
  • the total content of the epoxy resin and the epoxy resin curing agent in the adhesive composition is 10 parts by mass or less and 5 parts by mass with respect to 100 parts by mass of the total of component A, component B, component C and component D. The following is preferable. When the total content of the epoxy resin and the epoxy resin curing agent exceeds 10 parts by mass, the dielectric properties tend to be inferior.
  • the adhesive composition may further contain components other than the above-mentioned components A to D as long as the effects of the present technology are not impaired.
  • other components include an organic solvent, an adhesive-imparting agent such as a silane coupling agent, and a filler for adjusting fluidity and imparting flame retardancy.
  • the organic solvent is not particularly limited, and examples thereof include an alcohol solvent, a ketone solvent, an ether solvent, an aromatic solvent, and an ester solvent. Among these, aromatic solvents and ester solvents are preferable from the viewpoint of solubility.
  • the organic solvent may be used alone or in combination of two or more.
  • the adhesive composition radically cures the unsaturated bond at the terminal. It is preferable that it contains substantially no peroxide as a catalyst for promoting the reaction.
  • the total content of peroxides in the adhesive composition is preferably 0.01% by mass or less, more preferably 0.001% by mass or less. With such a configuration, the adhesive composition does not substantially crosslink the modified polyphenylene ether resin by heating, so that the glass transition temperature after curing can be easily lowered and the bending resistance can be improved. .
  • the peroxide include organic peroxides, and specific examples thereof include dicumyl peroxide and dilauroyl peroxide.
  • the thermosetting adhesive sheet according to the present technology has a film shape in which a thermosetting adhesive layer made of the above-mentioned adhesive composition is formed on a base material.
  • the thermosetting adhesive sheet is prepared, for example, by diluting the above-mentioned adhesive composition with a solvent and using a bar coater, a roll coater, or the like so that the thickness after drying is 10 to 60 ⁇ m, at least one surface of the base material. It is obtained by applying to and drying at a temperature of about 50 to 130 ° C.
  • the base material for example, a peeling base material obtained by subjecting a base material such as a polyethylene terephthalate film or a polyimide film to a peeling treatment with silicone or the like can be used, if necessary.
  • the thickness of the thermosetting adhesive layer constituting the thermosetting adhesive sheet can be appropriately set according to the purpose, but as an example, it can be 1 to 100 ⁇ m, or 1 to 30 ⁇ m.
  • thermosetting adhesive layer constituting the thermosetting adhesive sheet is made of an adhesive composition having a low dielectric constant and dielectric adjunct even after thermosetting and having good bending resistance even after thermosetting, for example. It can be applied to an interlayer adhesive for a flexible printed wiring board, or for bonding and fixing a terminal portion of a flexible printed wiring board and a connecting base material for lining the terminal portion.
  • thermosetting adhesive sheet has good peel strength after heat curing, heat resistance, and storability at room temperature.
  • the printed wiring board according to the present technology has a wiring pattern side of a base material with wiring having a base material and a wiring pattern, and a coverlay, via a cured product of the adhesive composition (thermosetting adhesive layer) described above. Are stacked.
  • a thermosetting adhesive layer of a thermosetting adhesive sheet is arranged between the wiring pattern side of the base material with wiring and the coverlay, and thermocompression bonding is performed to form the base material with wiring and the coverlay. It is obtained by integrating with.
  • the base material with wiring is excellent in electrical characteristics in the high frequency region, for example, it is preferable that the dielectric constant and the dielectric loss tangent are low in the frequency range of 1 to 10 GHz.
  • the base material include a base material containing any one of liquid crystal polymer (LCP: Liquid Crystal Polymer), polytetrafluoroethylene, polyimide and polyethylene naphthalate as a main component.
  • LCP Liquid Crystal Polymer
  • polytetrafluoroethylene polyimide
  • polyethylene naphthalate polyethylene naphthalate
  • a base material containing a liquid crystal polymer as a main component liquid crystal polymer film
  • the liquid crystal polymer has a very low hygroscopicity as compared with polyimide and is not easily affected by the usage environment.
  • the printed wiring board 1 shown in FIG. 1 includes a liquid crystal polymer film 2 and a copper foil 3 side of a base material with wiring (copper-clad laminate: CCL) including a copper foil (rolled copper foil) 3, and a liquid crystal polymer film 4. However, they are laminated via a cured product layer 5 made of the above-mentioned adhesive composition (thermosetting adhesive layer).
  • the printed wiring board may have a multi-layer structure as shown in FIG. 2, for example.
  • the printed wiring board 6 shown in FIG. 2 has a polyimide layer 7 (thickness 25 ⁇ m), a copper foil 8 (thickness 18 ⁇ m), a copper plating layer 9 (thickness 10 ⁇ m), a copper plating layer 9 side of a wiring board, and a coverlay. 10 (thickness 25 ⁇ m) is laminated via a cured product layer 5 (thickness 35 ⁇ m) made of the above-mentioned adhesive composition (thermosetting adhesive layer) (total thickness 201 ⁇ m).
  • Tough Tech H1221 Hydrogenated Styrene Thermoplastic Elastomer (Mw 120,000, Styrene Ratio 12%), Asahi Kasei Hybler 7125: Hydrogenated Styrene Thermoplastic Elastomer (Mw 110,000, Styrene Ratio 20%), Kuraray Tough Tech H1041 : Hydrogenated styrene-based thermoplastic elastomer (Mw 90,000, styrene ratio 30%), Tough Tech H1043 manufactured by Asahi Kasei Co., Ltd .: Hydrogenated styrene-based thermoplastic elastomer (Mw 110,000, styrene ratio 67%), manufactured by Asahi Kasei Co., Ltd.
  • OPE-2St2200 Modified polyphenylene ether resin having vinylbenzyl groups at both ends (Mn2,200), SA9000 manufactured by Mitsubishi Gas Chemicals, Inc .: Modified polyphenylene ether resin having methacryloyl groups at both ends (Mw1,700), SA120 manufactured by SABIC : Polyphenylene ether resin having hydroxyl groups at both ends, S201A manufactured by SABIC: Polyphenylene ether resin having hydroxyl groups at both ends, manufactured by Asahi Kasei Co., Ltd.
  • ⁇ Component C> 4032D Naphthalene type epoxy resin
  • DIC JER828 Epoxy resin
  • Mitsubishi Chemical YD014 Bisphenol A type epoxy resin, Nippon Steel & Sumikin Chemical Co., Ltd.
  • thermosetting adhesive composition Each component shown in Table 1 is weighed so as to have the mass shown in Table 1, and is uniformly mixed in an organic solvent containing toluene and ethyl acetate to form a thermosetting adhesive composition (thermosetting adhesive layer formation). Paint) was prepared.
  • thermosetting adhesive composition is applied to a polyethylene terephthalate film that has been subjected to a peeling treatment, and dried in a drying furnace at 50 to 130 ° C. to obtain a polyethylene terephthalate film and a thermosetting film having a thickness of 25 ⁇ m.
  • a thermosetting adhesive sheet having a sex-adhesive layer was produced.
  • thermosetting adhesive composition evaluation of coatability (film condition) of thermosetting adhesive layer forming paint>
  • the coatability of the thermosetting adhesive composition was evaluated according to the following criteria. The results are shown in Table 1.
  • thermosetting adhesive sheets prepared in Examples and Comparative Examples were laminated to prepare a test piece having a thickness of 1 mm, and then the test piece was heat-cured at 160 ° C. and 1.0 MPa for 1 hour for evaluation.
  • a test piece for use was prepared.
  • the permittivity at a measurement temperature of 23 ° C. and a measurement frequency of 10 GHz was determined using a dielectric constant measuring device (manufactured by AET). The results are shown in Table 1.
  • B Permittivity is 2.3 or more and less than 2.4
  • C Permittivity is 2.4 or more and less than 2.6
  • D Permittivity is 2.6 or more
  • Dissipation factor is less than 0.002
  • Dissipation factor is 0.002 or more and less than 0.0035
  • Dissipation factor is 0.0035 or more and less than 0.005
  • Dissipation factor is 0.005 or more
  • thermosetting adhesive sheet was cut into strips (2 cm x 5 cm) of a predetermined size, and the cut thermosetting adhesive layer was set on a liquid crystal polymer film having a thickness of 2 cm x 7 cm x 50 ⁇ m at 100 ° C.
  • the base material polyethylene terephthalate film
  • a rolled copper foil surface (roughening treatment) of a copper-clad laminate of the same size (CCL composed of a rolled copper foil having a thickness of 12 ⁇ m and a liquid crystal polymer film having a thickness of 50 ⁇ m) is applied to the exposed thermosetting adhesive layer.
  • the non-surface was overlapped from above and thermoset at 160 ° C. and 1.0 MPa for 1 hour. As a result, a sample was prepared.
  • the obtained sample was subjected to a 90-degree peeling test at a peeling speed of 50 mm / min, and the force required for peeling (initial peeling strength and peeling strength after the reliability test) was measured.
  • the results are shown in Table 1.
  • thermosetting adhesive sheet is cut into strips (1.5 cm ⁇ 12 cm) of a predetermined size, and the cut thermosetting adhesive layer is formed on a liquid crystal polymer film having a thickness of 1.5 cm ⁇ 12 cm ⁇ 50 ⁇ m at 100 ° C.
  • the base material polyethylene terephthalate film
  • the exposed thermosetting adhesive layer was superposed on FPC-TEG for MIT bending resistance test and heat-cured at 160 ° C. and 1.0 MPa for 1 hour.
  • the configuration of TEG11 for the MIT bending resistance test is shown in FIG.
  • copper wiring is formed from CCL composed of a liquid crystal polymer film (thickness 50 ⁇ m) as a base material and rolled copper foil (thickness 12 ⁇ m).
  • thermosetting adhesive sheets prepared in Examples and Comparative Examples were laminated to prepare a test piece having a thickness of 600 ⁇ m, and then the test piece was heat-cured at 160 ° C. and 1.0 MPa for 1 hour for evaluation.
  • a test piece for use was prepared. Using this test piece, the glass transition temperature that appears when the temperature is raised from -60 ° C to 250 ° C at a rate of 10 ° C / min using a dynamic viscoelasticity measuring device (manufactured by TA Instruments) is measured. I asked.
  • the modified polyphenylene ether resin (component B) having 75 to 90 parts by mass of the styrene elastomer (component A) and a polymerizable group at the terminal with respect to a total of 100 parts by mass of the adhesive composition. 3 to 25 parts by mass, and 10 parts by mass or less of the epoxy resin (component C) and the epoxy resin curing agent (component D) in total, and the styrene ratio of the styrene elastomer is less than 30%.
  • the product has a low dielectric constant and dielectric tangent even after thermosetting, and the glass transition temperature of the cured adhesive composition can be adjusted in the range of -40 to 40 ° C. Therefore, the product has good bending resistance. Do you get it.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
PCT/JP2019/030600 2019-08-02 2019-08-02 接着剤組成物、熱硬化性接着シート及びプリント配線板 WO2021024328A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201980098839.4A CN114174459B (zh) 2019-08-02 2019-08-02 粘接剂组合物、热固性粘接片以及印刷线路板
US17/629,932 US20220298396A1 (en) 2019-08-02 2019-08-02 Adhesive composition, thermosetting adhesive sheet, and printed wiring board
PCT/JP2019/030600 WO2021024328A1 (ja) 2019-08-02 2019-08-02 接着剤組成物、熱硬化性接着シート及びプリント配線板
JP2021538547A JP7322153B2 (ja) 2019-08-02 2019-08-02 接着剤組成物、熱硬化性接着シート及びプリント配線板
KR1020227002763A KR20220024998A (ko) 2019-08-02 2019-08-02 접착제 조성물, 열경화성 접착 시트 및 프린트 배선판

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2019/030600 WO2021024328A1 (ja) 2019-08-02 2019-08-02 接着剤組成物、熱硬化性接着シート及びプリント配線板

Publications (1)

Publication Number Publication Date
WO2021024328A1 true WO2021024328A1 (ja) 2021-02-11

Family

ID=74502859

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/030600 WO2021024328A1 (ja) 2019-08-02 2019-08-02 接着剤組成物、熱硬化性接着シート及びプリント配線板

Country Status (5)

Country Link
US (1) US20220298396A1 (zh)
JP (1) JP7322153B2 (zh)
KR (1) KR20220024998A (zh)
CN (1) CN114174459B (zh)
WO (1) WO2021024328A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003348462A (ja) 2002-05-27 2003-12-05 Olympus Optical Co Ltd カメラ及び撮像素子ユニット
TWI766342B (zh) * 2020-08-10 2022-06-01 大陸商鵬鼎控股（深圳）股份有限公司 電路板及其製備方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010261003A (ja) * 2009-05-11 2010-11-18 Asahi Kasei E-Materials Corp 回路接続用フィルム接着剤の製造方法
JP2011068713A (ja) * 2009-09-24 2011-04-07 Namics Corp カバーレイフィルム
JP2011228642A (ja) * 2010-03-31 2011-11-10 Furukawa Electric Co Ltd:The ウエハ加工用テープ
WO2012049873A1 (ja) * 2010-10-13 2012-04-19 電気化学工業株式会社 カバーフィルム
WO2014046014A1 (ja) * 2012-09-20 2014-03-27 株式会社クラレ 回路基板およびその製造方法
JP2015131866A (ja) * 2014-01-09 2015-07-23 ナミックス株式会社 エラストマー組成物、フィルムおよび半導体装置
WO2016117554A1 (ja) * 2015-01-19 2016-07-28 株式会社巴川製紙所 熱硬化性接着剤組成物、熱硬化性接着フィルム、および複合フィルム
JP2018001632A (ja) * 2016-07-04 2018-01-11 パナソニックＩｐマネジメント株式会社 樹脂付き金属箔、積層板、プリント配線板及び多層プリント配線板
WO2019151014A1 (ja) * 2018-02-05 2019-08-08 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6558790B1 (en) * 1999-11-30 2003-05-06 Avery Dennison Corporation Water vapor-permeable, pressure-sensitive adhesives
AU2002355051A1 (en) * 2001-11-30 2003-06-10 Ajinomoto Co., Inc. Method of laminating circuit board and method of forming insulation layer, multilayer printed wiring board and production method therefor and adhesion film for multilayer printed wiring board
JP2004231781A (ja) * 2003-01-30 2004-08-19 Asahi Kasei Electronics Co Ltd 硬化性ポリフェニレンエーテル系樹脂材料
JP2004263099A (ja) * 2003-03-03 2004-09-24 Asahi Kasei Electronics Co Ltd 硬化性ポリフェニレンエーテル系樹脂組成物
JP2004269785A (ja) * 2003-03-11 2004-09-30 Asahi Kasei Electronics Co Ltd 硬化性ポリフェニレンエーテル系複合材料
WO2007066763A1 (ja) * 2005-12-08 2007-06-14 Hitachi Chemical Co., Ltd. 電子部品用液状樹脂組成物及び電子部品装置
JP2007302817A (ja) * 2006-05-12 2007-11-22 Mitsubishi Engineering Plastics Corp 自動車外装部品製造用熱可塑性樹脂組成物
US10875283B2 (en) * 2014-07-31 2020-12-29 Toagosei Co., Ltd. Adhesive layer-equipped laminate, and flexible copper-clad laminate sheet and flexible flat cable using same
JP6458985B2 (ja) 2014-10-22 2019-01-30 ナミックス株式会社 樹脂組成物、それを用いた絶縁フィルムおよび半導体装置
JP6896993B2 (ja) 2015-09-18 2021-06-30 昭和電工マテリアルズ株式会社 樹脂組成物、プリプレグ、積層板及び多層プリント配線板
JP7107218B2 (ja) * 2016-07-20 2022-07-27 昭和電工マテリアルズ株式会社 樹脂組成物、樹脂層付き支持体、プリプレグ、積層板、多層プリント配線板及びミリ波レーダー用プリント配線板
US20180179424A1 (en) * 2016-12-23 2018-06-28 Industrial Technology Research Institute Adhesive composition and composite substrate employing the same
CN114127183A (zh) * 2019-07-17 2022-03-01 松下知识产权经营株式会社 树脂组合物、预浸料、带树脂的膜、带树脂的金属箔、覆金属箔层压板以及布线板
JP7351912B2 (ja) * 2019-08-06 2023-09-27 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010261003A (ja) * 2009-05-11 2010-11-18 Asahi Kasei E-Materials Corp 回路接続用フィルム接着剤の製造方法
JP2011068713A (ja) * 2009-09-24 2011-04-07 Namics Corp カバーレイフィルム
JP2011228642A (ja) * 2010-03-31 2011-11-10 Furukawa Electric Co Ltd:The ウエハ加工用テープ
WO2012049873A1 (ja) * 2010-10-13 2012-04-19 電気化学工業株式会社 カバーフィルム
WO2014046014A1 (ja) * 2012-09-20 2014-03-27 株式会社クラレ 回路基板およびその製造方法
JP2015131866A (ja) * 2014-01-09 2015-07-23 ナミックス株式会社 エラストマー組成物、フィルムおよび半導体装置
WO2016117554A1 (ja) * 2015-01-19 2016-07-28 株式会社巴川製紙所 熱硬化性接着剤組成物、熱硬化性接着フィルム、および複合フィルム
JP2018001632A (ja) * 2016-07-04 2018-01-11 パナソニックＩｐマネジメント株式会社 樹脂付き金属箔、積層板、プリント配線板及び多層プリント配線板
WO2019151014A1 (ja) * 2018-02-05 2019-08-08 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板

Also Published As

Publication number Publication date
US20220298396A1 (en) 2022-09-22
JP7322153B2 (ja) 2023-08-07
CN114174459B (zh) 2023-05-26
KR20220024998A (ko) 2022-03-03
CN114174459A (zh) 2022-03-11
JPWO2021024328A1 (zh) 2021-02-11

Similar Documents

Publication Publication Date Title
JP7090428B2 (ja) 接着剤組成物、熱硬化性接着シート及びプリント配線板
WO2021024364A1 (ja) 接着剤組成物、熱硬化性接着シート及びプリント配線板
CN106459704B (zh) 低介电性粘合剂组合物
CN111670236B (zh) 低介电粘合剂组合物
TWI490266B (zh) A resin composition for forming a bonding layer of a multilayer flexible printed circuit board, a resin varnish, a resin copper foil having a resin copper foil, a multilayer flexible printed circuit board, and a multilayer flexible printed circuit board
US20080113184A1 (en) Adhesive sheet
TWI743251B (zh) 樹脂組成物、使用該組成物之熱硬化性薄膜、樹脂硬化物、層合板、印刷配線板及半導體裝置
WO2021024328A1 (ja) 接着剤組成物、熱硬化性接着シート及びプリント配線板
JP4374395B1 (ja) 接着フィルム
JP2005144816A (ja) フレキシブル金属積層体
JP2009149829A (ja) 難燃性接着剤組成物ならびにそれを用いたカバーレイフィルムおよび接着シート
CN114514300B (zh) 粘接剂组合物、粘接片、层叠体以及印刷线路板
WO2002017695A1 (fr) Procede d'application de film
WO2017043455A1 (ja) 導電性接着剤組成物、導電性接着シート及びそれを用いた配線デバイス
TW202130766A (zh) 黏接薄膜、疊層體、以及印刷配線板
JPH09227659A (ja) エポキシ樹脂組成物、この樹脂組成物を用いたプリプレグ 及びこのプリプレグを用いた積層板
JP2008222906A (ja) フレキシブル配線板用接着剤組成物、ならびに、それを用いたカバーレイ、接着剤フィルム、フレキシブル銅張積層板、フレキシブル配線板および補強板付配線板
JPS63297483A (ja) フレキシブル印刷回路基板用接着剤組成物
JP2005248004A (ja) 半導体装置用接着剤組成物およびそれを用いたカバーレイフィルム及び接着剤シート並びに銅張りポリイミドフィルム
KR20200012505A (ko) 열경화성 접착제 조성물, 그의 경화물을 포함하는 적층필름, 및 상기 적층필름을 채용한 프린트 배선판
JPH11135901A (ja) 配線板材料及びプリント配線板
KR20170039502A (ko) 커버 레이 및 연성 인쇄 회로

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19940179

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021538547

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227002763

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19940179

Country of ref document: EP

Kind code of ref document: A1